Patent GB-771150-A (GB)
Title: Novel ethers and salts thereof and a process for the manufacture of same
IPC: C07D311/86
Filed: 1955-06-07
Abstract: The invention comprises compounds of the general formula <FORM:0771150/IV(b)/1> wherein Z is an oxygen or sulphur atom or the imino radical and R1 to R8 inclusive may be each a hydrogen atom or an alkyl radical or a halogen atom or a dialkylamino-alkoxy radical, at least one but not more than two of R1 to R8 being a dialkylaminoalkoxy radical and not more than two of them being halogen atoms, and salts thereof.  Such compounds are obtained by reacting a compound of the general formula <FORM:0771150/IV(b)/2> wherein r1 to r8 inclusive may each be hydrogen or an alkyl radical or a halogen atom or a hydroxy radical (at least one but not more than two of them being a hydroxyl radical and not more than two being halogen atoms) with a dialkylaminoalkyl halide in the presence of an acid acceptor and, where salts are required, treating the ether so formed with the appropriate acid or quaternizing agent.  The alkyl and alkoxy groups contain 1 to 6 carbon atoms.  Aralkylamino-alkoxy radicals referred to are dimethyl-aminomethoxy, dimethyl- and diethylaminoethoxy, 2-diethylaminopropoxy and di(sec.-hexyl) amino-ethoxy radicals. In forming mono- and poly - acid addition compounds, hydrochloric, hydrobromic, hydriodic, sulphuric, phosphoric, acetic, tartaric, oxalic, citric and ethane sulphonic acids are suitable.  To form mono- and poly-quaternary salts there may be used alkyl halides, dialkyl sulphates and aralkyl halides.  In Example (1) 4-hydroxyacridone-(9) and b -diethylaminoethyl chloride are reacted in chlorobenzene in the presence of sodium methoxide to form 4-(b -diethylaminoethoxy)-acridone-(9) which is converted to its di-hydrochloride and to its methobromide.  In a generally similar manner are prepared (2) 2 - (b  - diethylaminoethoxy) - acridone - (9) and its dihydrochloride; (3) 1-methyl-4-(b -diethylamino - ethoxy) - acridone - (9) and its dihydrochloride; (4) 1-chloro-4-(b -diethylaminoethoxy) - acridone - (9); (5) 1 - methyl - 4 - (b  - diethylaminoethoxy) - 6 - chloro - acridone - (9); (6) 1 - methyl - 2 - chloro - 4 - (b  - diethylaminoethoxy)-acridone-(9) and its dihydrochloride and methobromide; (7) 1,6-dichloro-4-(b -diethylamino-ethoxy)-acridone-(9); (8) 4-(b -diethylamino - ethoxy) - xanthone - (9); (9) 2-(b  - diethylamino - ethoxy) - xanthone - (9); (10) 2,7 - bis - (b  - diethylamino - ethoxy) - xanthone dihydrochloride; (11) 4-methyl-8-(b -diethylamino-ethoxy)-thioxanthone-(10); (12) 1-chloro - 4 - (b  - diethylamino - ethoxy) - thioxanthone-(10) and its monohydrochloride and mono-tartrate; (13) 1-chloro-2-methyl-4-(b -diethylamino-ethoxy)-thioxanthone-(10) hydrochloride; (14) 1,7-dichloro-4-(b -diethylaminoethoxy)-thioxanthone-(10). Halogen-containing initial materials in which Z represents the imino radical are obtainable by reacting o-chlorobenzoic acid or a halogenated-o-chlorobenzoic acid with a primary arylamine containing an ether group or a halogenoderivative thereof and converting the ether groups of the acridones obtained to hydroxy by hydrolysis in the presence of aluminium chloride.  Halogenated thioxanthones are obtained by reacting o-mercapto-benzoic acid or a halogenated o-mercapto-benzoic acid with a mercapto-ether or a halogenated mercapto-ether (e.g. 2-mercapto-anisole or 4-chloro-mercaptoanisole) and hydrolysing the ether groups in the resulting thioxanthone.  1 - Methyl - 2 - chloro - 4 - methoxy - acridone-(9) is prepared by heating the potassium salt of o-chlorobenzoic acid with 2-chloro-4-methoxy-5-aminotoluene in the presence of potassium carbonate and copper powder, and heating the resulting 2-(2-methoxy-4-chloro-5-methyl-anilino)-benzoic acid with polyphosphoric acid.  Heating the product with aluminium chloride in chlorobenzene gives 1-methyl-2-chloro-4-hydroxy-acridone - (9).  1 - Chloro - 2 - methyl - 4 - hydroxythioxanthone-(9) is obtained by reacting thiosalicylic acid with 4-chloro-3-methyl-anisole in sulphuric acid and heating with aluminium chloride the 1-chloro-2-methyl-4-methoxy-thioxanthone obtained.